Title:
The direct conversion of heat to
electricity using fast switching of
ferroelectric oxides
Related TechnologyFields:
Thermal Electric Generation
Principal Researcher:
Professor Richard D. James
james@umn.edu
Department of Aerospace Engineering and Mechanics
University of Minnesota, Minneapolis, MN 55455
tel. (612) 625-0706, fax. (612) 626-1558
Co-Principal Investigator:
Professor Bharat Jalan
bjalan@umn.edu
Department of Chemical Engineering and Materials Science,
University of Minnesota, Minneapolis, MN 55455
tel. (612) 625-4088, fax. (612) 626-7246
Brief Declaration of
Confidential Information
N/A
I.
Project Design
1.1 Executive Summary
The discovery of new methods of generating energy without adversely affecting the
environment is the most compelling scientific problem of our time. This proposal is based on the
most promising of a completely new family of methods for the direct conversion of heat-toelectricity discovered at the University of Minnesota1. Here, “direct” means that there is no
separate electrical generator: the material alone does energy conversion and generation of
electricity. Briefly, the material is the machine2.
In this proposal we outline a pathway to develop energy conversion devices based on phase
transformation in ferroelectric films. Importantly, this family of methods of energy conversion is
well suited to convert heat to electricity in situations where the heat is available at relatively
small temperature difference, implying broad potential applications, and significant commercial
impact. To help us guide applications of this work, we have partnered with Daikin Applied
(formerly McQuay International), with world headquarters at 13600 Industrial Park Blvd,
Plymouth, MN, the second largest manufacturer of air conditioning systems. Their systems
produce a lot of waste heat in the small temperature difference regime. A letter of collaboration
from Todd J. Love, Vice President of Engineering, is attached to this proposal.
In a nutshell, our concept relies on the use of oxide crystals that undergo highly reversible
phase transformations from a strongly ferroelectric phase to a paraelectric phase upon heating.
As the crystal is cooled through the phase transformation it releases (latent) heat, transforms to
the ferroelectric phase, and develops a strong polarization. If this crystal is the dielectric of a
capacitor that is connected in parallel to a reference capacitor, it will draw charge from the
reference capacitor. Upon heating, the crystal absorbs heat while transforming to the nonferroelectric phase at a higher temperature (due to the Clausius-Clapeyron relation) and
simultaneously releases charge to the reference capacitor. The sloshing of this charge back and
forth between the active and reference capacitor through a load resistance constitutes the direct
conversion of heat to electricity (Figure 3). The ability of Jalan to synthesize thin, single
crystalline oxide films of exceptional quality ensures a high capacitance and high dielectric
breakdown strength, which makes this method particularly attractive. Our proposal also includes
the implementation of a method for exceptionally reversible and fast switching of the film, which,
as we explain, is also important for this technology.
1.2 Background
The proposed specific way of doing ferroelectric energy conversion is to our knowledge
completely new. However, our proposed method is related to a family of methods first
discovered at the University of Minnesota under previous support of the Initiative for Renewable
Energy & the Environment (IREE, project RO-0002-12). Under that support, we pursued the
idea of ferromagnetic rather than ferroelectric phase transformations for the direct conversion of
heat to electricity1. Our demonstration received worldwide attention, being reported on hundreds
of websites and publications. It has been featured twice on websites frequently used by the
National Science Foundation (at their invitation), Science3603 and Livescience3.
1 While we learned a lot about this method, and more generally about using phase
transformations for energy conversion, we were not able to convince the U of M to give us
intellectual property relating to this method. In fact, it was a completely new method. In the
meantime, following our initial discovery reported in 20111, our method has been pursued quite
widely in Europe. Very recently, a Swiss company, Swiss Blue Energy, has commercialized
exactly our technology http://www.swiss-blue-energy.ch/index.php?id=107&L=0(Video). In
addition it is being pursued very actively in Prof. Manfred Kohl’s group in Karlsruhe8.
We also have been pursuing basic research on the general concept, especially development
of the materials, with funding from NSF and a MURI program. Besides learning more about the
materials, we also studied in detail the thermodynamics of the method and the potential
efficiency and work output9,10. From these fundamental studies we now see that the ferroelectric
case (unpublished) is in fact more promising than the ferromagnetic case. There are three main
advantages: First, the basic method involves the separation of charge, rather than the creation
of dipoles, which ultimately can give larger power densities and larger thermodynamic efficiency
according to our predictions; second, the method is much better adapted to miniaturization by
avoiding the presence of relatively large biasing permanent magnets and bulky coils, and
therefore has the potential to develop compact power sources, which can recover waste heat
from computing devices; third, the heat
transfer problem strongly favors a thin
film-based geometry, which is favored in
the ferroelectric case but strongly
disfavored in the magnetic case due to
demagnetization effects1. Shortly after
this time, Jalan (co-PI of this proposal)
joined the University of Minnesota. His
synthesis methods11-14 are ideal for
making
exceptionally
high-quality
ferroelectric oxide thin film needed to
demonstrate this method and to put it into
practice.
4
A key aspect of the use of first-order Figure 1: Recent demonstration of reversibility
phase
transformations
for
energy of stress-induced full phase transformation, under
conversion is the ability to control the demanding conditions of 400 MPa peak tensile
(each
cycle),
in
the
alloy
hysteresis of the phase transformation, stress
as this is the most important source of Ti54.7Ni30.7Cu12.3Co2.3. Cycle 1 is plotted on the
energy loss in the methods proposed same diagram as cycle 10 million. This alloy sathere. An alloy development method for isfies to high accuracy the cofactor conditions thedramatically lowering hysteresis due to orized by one of the PIs to lead to exceptional
5-7
James’
group5,15,16
was
already reversibility
developed in 2011, but the number of new low hysteresis alloy systems has steadily
increased17, and record low hysteresis levels (among materials with big first-order phase
transformations, i.e., > 5% strain) have been achieved since then in James’ lab7,9. This
2 procedure is based on satisfying strong conditions of geometric compatibility between phases
by systematic compositional changes. James’ group also theorized that a second level of
conditions called the cofactor conditions would further lower hysteresis as well as improve the
reversibility of the phase transformation17.
Reversibility of the phase transformation has been a pervasive bottleneck, hampering the
use of strong first order phase transformations in many areas of technology. Even the most
widely used phase-transforming material, binary NiTi, has significant migration of transformation
temperature, typically ∼20 °C, after a few hundred cycles, and exhibits complete failure after a
few thousand cycles under stress-induced transformation with stress levels as shown in Figure
1. Nevertheless, by only allowing long term cycling with very small strains, and restricting full
transformation to just a few cycles, the NiTi-based medical device industry (led by Medtronic
and Boston Scientific) is a very rapidly growing $5 billion industry.
This limitation has recently been breached in a remarkable way. An alloy has just
emerged4,6 (see Figure 1) that demonstrates a new route to multimillion cycles repeatability of
phase transformations, resolving the key limitation of “multiferroism by phase transformation”.
This alloy closely satisfies the cofactor conditions developed by James5. This is the second alloy
found that satisfies the cofactor conditions. The first alloy Zn0.45Au0.30Cu0.25 was developed in
James’ laboratory by systematic changes of composition7. It exhibits the lowest hysteresis
(1/2)(As + Af − Ms − Mf) ≈ 0.2 °C measured in a bulk alloy with a strongly first-order phase
transformation (> 5% transformation strain). These truly revolutionary developments pave the
way to the widespread use of phase transforming materials in technology, and in particular for
energy conversion devices6, which will be fully embraced in our proposed work.
1.3 Commercial and Environmental Impact
Besides the exciting long term possibility of using our devices to produce energy from the
enormous natural reserves stored on earth at small temperature difference, we argue that the
best near term application of this method is the conversion of waste heat-to-electricity from the
industrial sector, internal combustion
engines, power plants, computers and
hand-held
electronic
devices.
According to a 2008 DOE report18 on
waste heat recovery, the US industrial
sector alone consumes on average
over a terawatt (1.07 × 1012 W) of
power, representing about 1/15 of the
total average consumption of power
from all sources worldwide. This report
estimates that 25 − 50% of this power
is rejected as waste heat. This rejected Figure 2: Thermodynamic efficiency (Carnot, ideal,
heat is an ideal target for our family of in red) and nominal (dashed, blue) vs. temperature.
devices,
and
the
temperature Most industrial waste heat is produced at
difference between the rejection temperatures between 50 °C and 250 °C
3 temperature and ambient temperature is in the small temperature difference regime (Figure 2),
and is in a suitable temperature range for our proposed materials and devices.
As concluded by this DOE report18, “The waste heat streams analyzed in this study showed
that roughly 60% of unrecovered waste heat is low quality (i.e., at temperatures below 450◦ F
[232 °C]). While low temperature waste heat has less thermal and economic value than high
temperature heat, it is ubiquitous and available in large quantities. Comparison of total work
potential from different waste heat sources showed that the magnitude of low temperature
waste heat is sufficiently large that it should not be neglected in pursuing RD&D opportunities
for waste heat recovery”.
A similar potential exists in areas of waste heat production from automobiles, power plants
and computers. Automobiles produce exhaust gases in a similar temperature range as that seen
in industrial heat emission, while cooling water in the condenser of power plants emerges at a
little less than ∼100 °C. The waste heat of computers is a growing problem, also at the rapidly
expanding system of clusters containing many thousands of cores2. Currently, the energy
consumption at major data centers in the US is about 2.5% of the national energy budget,
corresponding to the energy used by two medium-sized cities. At smaller scales the conversion
of waste heat-to-electricity (that could help recharge the battery in hand-held electronic devices)
has significant commercial potential. The revolutionary opportunity here is the chip-level
integration of our technology via thin film versions of our devices. This, as well as opportunities
for solar thermal power applications of our ideas, drive the need for thin film devices: this
research is central to our program.
Most of the major existing solar thermal plants, such as the plants in the Mojave Desert or
Seville, Spain, have huge towers, boilers, heat exchangers, turbines, condensers and piping
systems to run the water or water/salt based energy conversion systems. In the family of
methods we propose, the heat is converted directly to electricity, eliminating the need for this
infrastructure. The solar flux concentrator systems in these facilities could potentially be
integrated with our methods. That is, the infrared radiation that is normally reflected by a bank
of mirrors to a black tank on the top of a tower, for steam-based energy conversion, could rather
be focused to a point near the mirror where one of our proposed energy conversion devices
resides. This would potentially make the whole system modular for distributed, residencebased, energy conversion. It should be noted that (water-based) cooling of solar thermal plants
has been problematic for both technical and environmental reasons.
Climate scientists tell us that, to avoid the predicted catastrophic impending 2°C in
temperature, it is not sufficient to make minor perturbations of existing fossil fuel based energy
conversion methods19. New zero-emission energy conversion alternatives will be needed. For
our method we supply below a challenging but carefully considered plan that also takes
maximum advantage of revolutionary scientific discoveries of the past year.
For a small part of waste heat, mainly extraction of energy from automobile exhaust gases
and computers, thermoelectric systems are most often discussed. Thermoelectric also converts
heat to electricity and are applicable to cases where the heat is stored at small temperature
difference. The performance of thermoelectric devices is measured by a figure of merit ZT. The
most often used thermoelectric material is Bi2Te320, having ZT~1. Despite an enormous long-
4 term investment by NASA, and more recently by DOE, useable materials with ZT significantly
larger than 1 have not emerged. It must be stressed that the major thermoelectric materials
were a product of the early space program, with the main thermoelectric properties of Bi2Te3
understood as early as 195720. A main goal of our program is the demonstration of a significant
improvement of both efficiency and power output over available thermoelectric devices.
Several major sources
of energy on earth are in a
temperature
range
that
could be accessed by our
devices. For example, the
~20 °C difference between
surface ocean temperatures
and temperatures just below
the thermocline in midlatitude waters is in an ideal
temperature range of our
materials. Even better, the
Figure 3: Schematic of ferroelectric energy conversion. A
temperature difference in
pulsed heat source is applied to ferroelectric thin film (d ≤ 1 µm)
the Arctic between ocean
capable of undergoing a highly reversible ferroelectric phase
temperature (≥ 0°C) and
transformation. The film is sandwiched between metal (Au)
ambient (−40° to −20°C for
electrodes and serves as an active capacitor. The battery Vbat is
most of the year) is in a
only used for initial charging and to compensate for possible
good
range
for
our
leakage of charge.
materials, and the overall
lower temperatures lead to increased efficiency for a given temperature difference. Ferroelectric
transformation temperatures are easily tuned to this range. The general family of methods of
energy conversion discussed in this proposal produce no greenhouse gases. Because these
methods are based on a cyclic process that moves heat from higher to lower temperatures, they
do not contribute to global warming.
The materials that we propose to study are nontoxic oxide materials. Our thin film synthesis
methods only involve CO2 production as part of the purification of the gases used to prevent (or
induce) oxidation, and the power needed for melting, processing and device construction.
1.4 Direct Conversion of Heat-to-Electricity using Ferroelectric Phase Transformations
Referring to the schematic Figure 3, the basic idea we propose is the following. A capacitor
comprised of a ferroelectric film is subject to a rapidly oscillating temperature that passes above
and below the transformation temperature of the film. The film undergoes a highly reversible,
low hysteresis ferroelectric phase transformation optimized to give a large change of
capacitance. We have analyzed this in detail, but these details are not disclosed for possible
intellectual property considerations. To our knowledge this idea has not been studied previously.
The most important point to make is that the first-order character of the phase
transformation is critical for these devices. This feature implies the existence of a mixed phase
5 region in the temperature-entropy diagram for this process9,10, which permits high efficiency
Carnot cycles. This is the solid-state analog of the well-known fact that steam generation
(currently the overwhelming choice) is used for energy production rather than single-phase (say)
gas generators. The latter support Carnot cycles, but these only give a comparable amount of
work per cycle if the working temperature difference is exceedingly high. The significant
opportunity for solid-state phase transformations is that they are adapted to the small
temperature difference regime of much natural and waste heat. The first order character of the
phase transformation is also a main feature of our previously studied method of ferromagnetic
energy conversion, as well as the most promising emerging magnetocaloric and electrocaloric
refrigeration devices.
We find several critical advantages of ferroelectric energy conversion over ferromagnetic
energy conversion. First, there is the ease in broad classes of films of moving the heat very
quickly in and out of the material, particularly in the thin films (d ≤ 1 µm) synthesized by Jalan.
As in the ferromagnetic case, it is necessary to have a switch, and this is included as one of our
key tasks. Two other key advantages of thin, high quality, single-crystalline oxide film is that
capacitance goes as 1/d, so high values of capacitance are possible as compared to the bulk,
and the high quality films of Jalan also mitigate against dielectric breakdown. With Jalan’s hybrid
MBE film growth methods11-14,21 (developed in the context of microelectronic/optical materials),
exceptionally high values of capacitance are already demonstrated using thin films22. The only
study of the effect of field on transformation temperature in ferroelectrics is that of Moya et al.23
in bulk material (0.5-mm-thick crystal).
We note that while thinness of film (and therefore fast heating and cooling) is a big
advantage for ferroelectric case, it is a problem with ferromagnetic energy conversion. That’s
because the rapid change of magnetization M at the transformation is partitioned between the
magnetic induction B and the magnetic field H via the dipolar relation B = H + M. But only
changes of B deliver to electrical energy via Faraday’s law. However, for the thin film geometry,
almost all of the changes of M are converted into changes of H, rather than B (i.e., dM/dt ≈ dH/dt).
To make this method of energy conversion method a reality, we propose a systematic
development based on the five tasks listed below.
1.4.1 (Task 1): Development of an Oxide Film with a λ2 = 1 Interface
First, we need a highly reversible oxide film with a low hysteresis ferroelectric transformation
and a suitable transformation temperature, typically 10 - 100 °C above room temperature. We
first note that transformation temperatures are highly tunable and there exist several suitable
starting points for material development by compositional changes24.
Simultaneously, to achieve both a highly reversible transformation and a method of fast
switching (see below), we propose to develop an oxide satisfying to high accuracy the condition
λ2 = 1 described above. We have extensive experience doing this type of materials discovery
work in other cases15,25,26. Such a material opens the way for revolutionary methods of fast
switching. The concept we propose to investigate is the following. When λ2 ≠1 a broad stressed
transition layer separates the two phases. In materials that do not have an exceptionally soft
6 modulus, this layer typically undergoes a dramatic reduction to atomic dimensions as λ2 → 1.
This is illustrated in High Resolution Transmission Electron Microscopy (HRTEM) in Figure 4(a).
The measured interface normal n ‖ (755) in this case also agrees well with one of the two
theoretical solutions of the condition of compatibility in this case.
Figure 4: (a) High resolution transmission electron micrograph27 of a perfect interface (dashed)
between phases in a material (Ti0.50Ni0.4025Pd0.0925) tuned to satisfy precisely λ2 = 1, and (b)
corresponding theoretical prediction, having excellent agreement with the measurements in (a).
(c) Concept for fast switching in which a defect-free perfect interface is arranged to be parallel to
the substrate of film and therefore only has to travel the thickness of the film.
This set-up suggests our strategy. Miscut a substrate that is lattice matched to the (typically
cubic) parent phase precisely on the λ2 = 1 interface plane. In the case of Figure 4 the substrate
would be miscut on the
(755) plane. This will allow exceptional switching speeds even with
accepted modest values for speeds of interfaces, because the
interface needs only to traverse
the thickness of the film. The geometry shown in Figure 4 is suitable for fast and potentially
unprecedented switching times in devices. For example, being a perfect interface between
phases, one could assume that a λ2 = 1 interface could have kinetics similar to that of a twin
boundary. Faran and Shilo28 have measured speeds of twin boundaries of about 2CT ≈ 6000
m/s, where CT is the shear wave speed, in BaTiO3 single crystals. For an interface traversing a
film of thickness 1 µm at 6000 m/s, a switching time of 6 nanoseconds achieves a fully
transformed film. We note that Faran and Shilo28 actually employed electrically driven twin
boundaries, by making use of the different preferred directions of polarization in the two variants
of the twin. Fast switching directly translates into high power output for an energy conversion
device.
Essential to this concept is to discover a λ2 = 1 ferroelectric phase transformation, which we
propose to do this using hybrid MBE synthesis methods of Jalan. From data of Jaffe24 p. 94),
BaTiO3 offers an outstanding starting point for the tuning of lattice parameters to make λ2 = 1. In
particular, BaTiO3 has three ferroelectric phase transformations with abrupt changes of
ferroelectric properties. Based on accepted measured lattice parameters, we have calculated29
7 the value of λ2 for all three transformations, and we obtain the values λ2 = 0.998 (cubic to
tetragonal), λ2 = 1.00416 (tetragonal to orthorhombic), and λ2 = 0.9978 (orthorhombic to
trigonal). Based on our previous work, these values indicate outstanding starting points for
tuning. As collected in Jaffe24, isovalent substitutions of Pb, Ca, Sr, Zr, Hf and Sn in BaTiO3
preserve one or more of these transformations out to about 20 atom %. As a starting point, we
will focus on substitutions of Sn and Zr at the B-site and Ca and Sr at the A-site. As shown by
Jaffe, these particular substitutions only have a modest effect on transformation temperature.
Another attractive aspect of the ferroelectric thin film concept is that a high volumetric
energy density, εV2/2d2, where ε is the permittivity, V is the applied voltage and d is thickness of
dielectric, can be achieved by using thin films. For instance, a parallel plate active capacitor with
BaTiO3 as a dielectric medium of thickness 200 nm and with an applied voltage of 4V, will
posses an energy density of 106 Joule/m3 (These values have been achieved30).
1.4.2 (Task 2): Development of a Switch
A key aspect of the proposed method is the need to oscillate the temperature, and this
feature is enabled by a fast switch. Mechanical switches are possible, such as a spinning device
(as we developed in our earlier IREE project and now used by Swiss Blue Energy, see above)
or a cantilever that oscillates near a warm surface as investigated in detail by M. Kohl and his
group31. We also will consider optical switches in the infrared, which are undergoing extensive
study and development in other areas.
1.4.3 (Task 3): Modeling of Thermo-Electro-Dynamics of Ferroelectric Energy Conversion
For much of the work described above, including the recent breakthroughs on the
reversibility of phase transformations4,6,7 and our work on ferromagnetic energy conversion1,
careful theoretical predictions preceded and guided synthesis. We intend to continue this
approach here to guide our designs and oxide film development. In particular this will include
rigorous modeling of the ferroelectric phase transformation and of the thermodynamics of this
method of energy conversion, including electro-dynamic considerations, and accurate modeling
of heat transfer. Predictions of both efficiency and power density are included so as to make
careful comparisons with alternative methods in the literature. As devices, or parts of devices
are developed, predictions will be rigorously compared to measured behavior to test and guide
improvements to the theory.
1.4.4 (Task 4): Construction and Testing of a Prototype
The films made by Jalan can be easily electroded, as this is a standard procedure used by
Jalan for dielectric and electric characterization. Thus, the form needed for demonstration of the
technology – a thin ferroelectric film in a capacitive arrangement – is immediately available after
synthesis. Thus, upon completion of the task involving materials development, we are able to
make a prototype for testing, while developing a switch in parallel. This will allow us to make an
experimental assessment of the technology in a timely fashion, according to our year-to-year
milestones. It will also allow us to test ideas for a switch on a working prototype. In addition, it
8 will allow us to make critical comparisons between theory and experiment so as to calibrate our
model.
1.4.5 (Task 5): Scale-up
While a subfamily of our potential applications – the recovery of waste heat (and essential
cooling) from computer cores in data centers and from hand held electronic devices (so as to
offset battery discharge) – may involve the use of single films on a wafer, larger scale
applications will require many films and there are scale-up issues. In the final year of this project
we will study methods of scaling up the technology. A key aspect of scale-up is whether
unforced environmental cooling is sufficient for the application or whether forced cooling is
needed. In the latter case the interaction of nearby devices particularly needs to be considered.
II. Project Management
2.1 Collaboration and Institutional Partnership
For potential industrial applications involving the heat emitted from AC systems, we have
partnered with Daikin Applied, 13600 Industrial Park Blvd, Plymouth, MN, the second largest
manufacturer of air conditioning systems (Carrier Corporation is first). Their systems produce a
lot of waste heat in the small temperature difference regime that directly relates to our proposed
method of energy conversion. An important aspect of this collaboration is their willingness to
share available data about their systems, which will guide important decisions about our
development, as measured and predicted data about our method becomes available. A letter of
collaboration from Todd J. Love, Vice President of Engineering, is attached to this proposal.
Within the University of Minnesota, we have partnered with Michael J. Gust, Industry Liaison
Officer of the NSF sponsored Center for Compact and Efficient Fluid Power (and former VP of
Corporate Engineering at McQuay), CCEFP. Mike has been extremely helpful pointing out
useful internal and external partners for us relating to the proposed research in preparation for
larger potential projects with agencies such as ARPA-E. Besides experts in heat and mass
transfer in CCEFP, other potentially valuable collaborators at the University of Minnesota for
larger projects are recently hired faculty Xiaojia Wang (Department of Mechanical Engineering,
CSE; expert in microscale heat transfer) and Brad Holschuh (Department of Design, Housing &
Apparel, College of Design; expert in phase transformations for use in wearable technology).
We propose to take full advantage of the programs of IonE to connect us to a broad
collection of experts on environmental science, energy conversion, climate change, and human
and legal aspects of energy conversion.
These collaborations will be useful as we seek larger projects for this research. While
obvious targets are NSF (MPS, DMR, SEES), ARPA-E (open solicitation, programs on efficient
buildings, energy conversion) and DOE (BES, materials discovery), there are also significant
opportunities with NASA (space-based energy sources, the all-electric airplane), and DoD
(compact power sources, sensors) agencies.
2.2 Monitoring and Evaluation Scheme
9 The PIs Jalan and James will work closely together and will hold bi-weekly joint meetings
that will include graduate students and postdocs engaged with the work. These graduate
students/postdocs will formally report on research progress during the previous two weeks. The
research itself is consistent with IonE’s stated mission of offering solutions, and a necessary
condition for participation in this research will be that these students participate in the full range
of programs offered by IonE. The PIs will also take advantage of programs and opportunities of
IonE. The PIs have the strong view that education on the broad implications of environmental
research is a shared responsibility of academic research on energy conversion devices. During
these bi-weekly meetings, the PIs will also review progress vis-à-vis the five tasks and the yearto-year milestones given in this proposal.
The PIs will report the results of this research with disclosure of IonE support in the highestlevel technical journals devoted to energy science, materials science and applied physics. In
addition to technical articles the senior PI has been active in writing perspective and popular
articles on breakthroughs in materials science in broadly visible venues6,32,33, and this will be
continued as part of the present research but with co-authorship of both PIs.
The PIs will meet on a regular basis with technical personnel from Daikin Applied, on a
schedule that is consistent with their needs and wishes. As seen from the attached letter of
Todd Love, they are enthusiastic to work with us. The PIs will make every effort to secure
intellectual property associated to discoveries generated by the project. The senior PI has
already discussed the proposed method of ferroelectric energy conversion with Eric S. Olson of
OVPR. Complete reports as requested by IonE will be prepared on a timely basis.
2.3 Year-to-year Milestones
Year 1: Development of ferroelectric oxide films with a λ2 = 1 interface using the hybrid MBE
approach including extensive structural characterizations using high resolution X-ray diffraction,
X-ray spectroscopy, scanning TEM, electron energy loss spectroscopy. A complete
thermoelectrodynamic analysis of the ferroelectric energy conversion device proposed above.
Year 2: Adapt the growth procedure of year 1 to the miscut substrates, cut on the calculated
perfect interface associated to λ2 = 1. Grow all-epitaxial MIM capacitors including dielectric and
electrical characterizations. Develop rapid heating/cooling and automatic methods for this
concept by building a switch.
Year 3: Develop, analyze and test a prototype of a ferroelectric energy conversion device
designed for heat-to-electricity conversion. Scale-up. Identify most promising applications.
III. Detailed Project Budget
We request $250K/year for three years. Funds equivalent to two grad students ($99,508/year) &
two-post docs ($110,492/year) are requested for each of the 3 years. $10K/year is requested to
travel to (MRS, ARPA-E) annual meetings. Funds in the amount of $30K/year are requested to
defray costs of purchasing materials, basic lab supplies and characterization facilities. 10 III.
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References
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020606 (2015).
R. Zarnetta, R. Takahashi, M. L. Young, A. Savan, Y. Furuya, S. Thienhaus, M. Rahim B.
Maa, J. Frenzel, H. Brunken, Y. S. Chu, V. Srivastava, R. D. James, I. Takeuchi, G. Eggeler,
and A. Ludwig, Adv. Func. Mater. 20, 1917 (2010).
R. D. James and Z. Zhang, in Magnetism and Structure in Functional Materials, Springer
Series in Mater. Sci. 79, 159 (2005).
X. Chen, Y. Song, N. Tamura, and R. D. James., Submitted to Ortiz Volume of J. Mech.
Phys. Solids arXiv:1501.05064 [cond-mat.mtrl-sci], (2015).
Waste Heat Recovery: Technology and Opportunities in US Industry.
R. J. Barthelmie and S. C. Pryor, Nature Climate Change 4, 684 (2014).
C. B. Satterthwaite and R. Ure, Phys. Rev. 108, 1164 (1957).
P. Xu, T. C. Droubay, J. S. Jeong, K. A. Mkhoyan, P. V. Sushko, S. A. Chambers, and B.
Jalan, Adv. Mater. Interfaces, 1500432 (2015).
E. Mikheev, A. P. Kajdos, A. J. Hauser, and S. Stemmer, Appl. Phys. Lett. 101, 252906
(2012).
X. Moya, E. S. Taulats, S. Crossley, D. G. Alonso, S. K. Narayan, A. Planes, L. Manosa, and
N. D. Mathur, Adv. Mater. 25, 1360 (2013).
B. Jaffee, W. R. Cook Jr., and H. Jaffe, Piezoelectric ceramics. (Academic Press Inc., New
York, 1971).
J. Cui, Y. S. Chu, O. Famodu, Y. Furuya, J. Hattrick-Simpers, R. D. James, A. Ludwig, S.
Thienhaus, M. Wuttig, Z. Zhang, and I. Takeuchi, Nat. Mater. 5, 286 (2006).
V. Srivastava, X. Chen, and R. D James, Appl. Phys. Lett. 97, 014101 (2010).
11 27
28
29
30
31
32
33
R. Delville, S. Kasinathan, Z. Zhang, J. V. Humbeeck, R. D. James, and D. Schryvers, Phil.
Mag. 90, 177 (2010).
E. Faran and D. Shilo, Phys. Rev. Lett. 104, 155501 (2010).
V. Srivastava, R. Takahashi, I. Takeuchi, and R. James, Unpublished notes (2015).
K. J. Choi, M. Biegalski, Y. L. Li, A. Sharan, J. Schubert, R. Uecker, P. Reiche, Y. B. Chen,
X. Q. Pan, V. Gopalan, L.-Q. Chen, D. G. Schlom, and C. B. Eom, Science 306, 1005
(2004).
M. Kohl, M. Gueltig, V. Pinneker, R. Yin, F. Wendler, and B. Krevet, Micromachines 5, 1135
(2014).
R. D. James, Nature 521, 298 (2015).
R. D. James, SIAM News, 14 (2014).
12 IV.
CVs of the Principal Researchers
Richard D. James
Distinguished McKnight University Professor
Department of Aerospace Engineering and
Mechanics, University of Minnesota
Minneapolis, MN 55455
a. Professional Preparation
Brown University
The Johns Hopkins University
University of Minnesota
james@umn.edu
http://www.aem.umn.edu/~james/research/
Sc.B. (Biomedical Engineering)
Ph.D. (Mechanical Engineering)
Postdoc (Mathematics/Materials)
b. Appointments
Visiting Professor, Mathematics Institute, Oxford University
Russell J. Penrose Professor, University of Minnesota
Copernicus Visiting Scientist, University of Ferrara (1 month)
Humboldt Senior Research Fellow (Humboldtpries),
John von Neumann Professorship, TU Munich (2 months)
Mary Shepard B. Upson Visiting Chair, Cornell University
Rothschild Visiting Professor, Cambridge University
1999
Distinguished McKnight University Professor, University of Minnesota
Member, Institute for Advanced Study, Princeton
Professor, Department of Aerospace Engineering and Mechanics, Minnesota
Associate Professor, Department of Aerospace Engineering and Mechanics
Assistant Professor, Division of Engineering, Brown University
1974
1979
9/79-1/81
2013-2014
2001-2011
2010
2006-2007
2006
2002
19981993-1994
19911985-1991
1981-1985
c. Selected publications
Five publications most closely related to proposed project:
• R. D. James, Taming the temperamental metal transformation, Science 348, 968-969 (2015).
• Y. Song, X. Chen, V. Dabade, T. W. Shield and R. D. James, Enhanced reversibility and
unusual microstructure of a phase-transforming material, Nature 502, 85-88 (2013).
• V. Srivastava, Y. Song, K. Bhatti and R. D. James, The direct conversion of heat to electricity
using multiferroic alloys, Advanced Energy Materials (by invitation) 1, 97-104 (2011).
• Xian Chen, Vijay Srivastava, Vivekanand Dabade, and R. D. James, Study of the cofactor
conditions: conditions of supercompatibility between phases, J. Mech. Phys. Solids 61, 25662587 (2013).
• 5. K. Bhattacharya and R. D. James, The material is the machine, Science 307, 53 (2005).
Five other significant publications:
• R. D. James, Magnetic alloys break the rules, Nature 521, 298-299 (2015).
13 • S. Yuan, P. L. Kuhns, A. P. Reyes, J. S. Brooks, M. J. R. Hoch, V. Srivastava, R. D. James, S.
El-Khatib, and C. Leighton, Magnetically nanostructured state in a Ni-Mn-Sn shape-memory
alloy, Phys. Rev. B 91, 214421 (2015).
• A. S. Banerjee, R. S. Elliott, R. D. James, A spectral scheme for Kohn-Sham density functional
theory of clusters, http://arxiv.org/abs/1404.3773, J. Computational Physics, 226-253 (2015). • Vijay Srivastava, Xian Chen and R. D. James, Hysteresis and unusual magnetic properties in
the singular Heusler alloy Ni45Co5Mn40Sn10, Applied Physics Letters 97, 014101 (2010).
• R. D. James and M. Wuttig, Magnetostriction of martensite, Phil. Mag. A 77, 1273 (1998).
d. Synergistic activities
2015 Southwest Mechanics Lecture Series (Austin, Texas A&M, Houston); Panorama of
Mathematics (Hausdorff Institute, Bonn); Colorado School of Mines Distinguished Lecture;
Plenary Lecture – ESOMAT; Lecture Series, Eighth Summer School in Analysis and Applied
Mathematics, Rome (3 lectures). Public lecture: “New materials: real and imagined”, Antwerp.
2014 Park City/IAS Summer Mathematics Program: Five lectures on “Phase transformations,
hysteresis and energy conversion: the role of geometry in the discovery of materials”;
“Landscapes of Mathematics” series, University of Bath; Theodore von Karman Prize Lecture,
SIAM Annual Meeting; “Materials from Mathematics” (SIAM News, November 3, 2014). 2005 - 2014 17 Plenary Lectures, 10 Lecture Series. Also: James R. and Shirley A. Kleigel
Lecture (Caltech), Crocco Colloquium (Princeton), Penrose Lecture (UMN), ICMSE Lecture
Series (AFRL), Heinz Gumin Prize Ceremony (Munich), MMM (invited), Aziz Lectures (UMD),
Mork Family Lecture (USC), J. K. Knowles Lecture (Caltech), Energy Threats (MITRE), Mandel
Lecture (Ecole Polytechnique), Pedro Nunes Lecture (Lisbon).
1999 - Chief Editor, with Sir J. M. Ball, Archive for Rational Mechanics and Analysis
1997 - Editorial Advisor, Journal of the Mechanics and Physics of Solids
e. Collaborators, Advisors, Advisees
Collaborators (past 48 months) and Co-editors (past 24 months). Total: 62. A. Agrawal
(Northwestern), B. Audoly (Paris 6), J. Ball (Oxford), K. Bhattacharya (Caltech), C. Bouman
(Purdue), M. C. Boyce (Columbia), J. Buschbeck (UCSB), A. N. Choudhary (Northwestern), R.
J. Clifton (Brown), M. Comer (Purdue), K. Dayal (CMU) A. DeSimone (SISSA), V. S. Deshpande (Cambridge) T. Dumitrica (Minnesota), G. Eggeler (Bochum), N. A. Fleck (Cambridge), I.
Fonseca (CMU), L. B. Freund (UIUC), G. Friesecke (Munich), H. Gao (Brown), E. Van der
Giessen (Groningen), P. R. Guduru (Brown), S. Haile (Caltech), V. Humbeeck (Leuven), J. W.
Hutchinson (Harvard), S. Kalidindi (Gatech) D. Kinderlehrer (CMU), R. Kohn (Courant), E. Kuhl
(Stanford) Jiangyu Li (U. Washington), C. Leighton (UMN), G. Leoni (CMU), A. Ludwig (Bochum),
M. Luskin (Minnesota), S. Mu ̈ller (Bonn), R. Narasimhan (IISc Bangalore), M. Ortiz (Caltech), H.
Owhadi (Caltech), C. Palmstrøm (UCSB), T. Pardoen (Louvain), R. Pego (CMU), E. Quandt
(Kiel), K. Rabe (Rutgers), G. Ravichandran (Caltech), J. R. Rice (Harvard), R. Rizzoni (Ferrara),
N. Schryvers (Antwerp), H. Shi (Antwerp), T. Shield (Min- nesota), J. Snyder (Caltech), V.
Sundararaghavan (Michigan), Z. Suo (Harvard), P. Suquet (Marseille), E. Tadmor (Minnesota),
I. Takeuchi (Maryland), W. Tirry (Antwerp), P. Voorhees (Northwestern), A. Voter (LANL), N.
14 Walkington (CMU), M. Wuttig (Maryland), Wei Yang (President, NSF of China), R. Zarnetta
(Bochum) Ph.D. advisor, J. L. Ericksen (ret.); postdoctoral sponsor, Roger Fosdick (ret.)
Postdoctoral sponsorship: past 5 years. (Full career: 30 Postdocs) V. Srivastava (GE Global
Research), K. Bhatti (GE Global Research), A. Kumar (Asst. Prof., IIT Delhi), Y. Hakobyan
(Postdoc, MIT), Y. Ganor (start-up, Boston), K. Dayal (Assoc. Prof., CMU), L. Liu (As- soc. Prof.,
Rutgers), H. van Lengerich (3M), A. Banerjee (LBL). X. Chen (Asst. Prof. HKUST). Ph.D. advisees. (Full career: 16 Ph.D. students) X. Liu (US–China trade), K. Bhattacharya
(Prof., Caltech), A. De Simone, (Prof., SISSA, Trieste), C. Chu (Learning Services, Notre Dame
de Namur, Belmont, CA), B. Berg (Boston Scientific), N. Simha (Medtronic), R. Tickle (start-up),
J. Cui (Prof., Iowa State) W. Falk (Medtronic), L. Liu, (Assoc. Prof., Rutgers), Z. Zhang
(EV3/Medtronic), S. K. Srivastava (microelectronics industry), K. Shankar (COMSOL), X. Chen
(Asst. Prof., HKUST), Y. Song (Lattice Engine). A. Banerjee (LBL). 15 Bharat Jalan
a. Professional Preparation
Indian Institute of Technology Madras, Materials Science, B. Tech. and M. Tech., 2006
University of California, Santa Barbara, Materials Science, Ph.D., 2011
b. Appointments
Assistant Professor, September 2011- present, Department of Chemical Engineering and
Materials Science, University of Minnesota -Twin Cities
c. Selected Publications
Five publications most closely related to proposed project:
•
•
•
A. Prakash, J. Dewey, H. Yun, J. S. Jeong, K. A. Mkhoyan and B. Jalan, “Hybrid
molecular beam epitaxy growth for stoichiometric BaSnO3”, J. Vac. Sci. Technol. A 33,
060608 (2015).
http://dx.doi.org/10.1116/1.4933401
T. Wang, A. Prakash, E. Warner, W. L. Gladfelter, B. Jalan, “Molecular Beam Epitaxy
Growth of SnO2 using a Tin Chemical Precursor”, J. Vac. Sci. Technol. A, 33, 020606
(2015). http://dx.doi.org/10.1116/1.4913294
K. Ganguly, P. Ambwani, P. Xu, J.S. Jeong, K.A. Mkhoyan, C. Leighton and B. Jalan,
“Structure and transport in high pressure oxygen sputter-deposited BaSnO3- ” APL
Materials 3, 062509 (2015) http://dx.doi.org/10.1063/1.4919969
P. Xu, D. Phelan, J.S. Jeong, K.A. Mkhoyan, and B. Jalan, Stoichiometry-driven Metalto-Insulator Transition in NdTiO3/SrTiO3 Heterostructures, Appl. Phys. Lett. 104, 082109
(2014)
T. Wang, K. Ganguly, P. Marshal, P. Xu, and B. Jalan, Critical thickness and strain
relaxation in MBE-growth SrTiO3 films, Appl. Phys. Lett. 103, 212904 (2013).
http://dx.doi.org/10.1063/1.4833248
δ
•
•
Five other significant publications:
•
•
•
•
•
J. S. Jeong, P. Ambwani, B. Jalan, C. Leighton, and K. A. Mkhoyan, “Observation of
electrically-inactive interstitials in Nb-doped SrTiO3”, ACS Nano, 7, 4487 (2013).
http://dx.doi.org/10.1021/nn401101y
A. Janotti, B. Jalan, S. Stemmer, and C. G. Van de Walle, “Effects of doping on the
lattice parameter of SrTiO3” Appl. Phys. Lett., 100, 262104 (2012).
http://dx.doi.org/10.1063/1.4730998
B. Jalan, S. J. Allen, G. Beltz, P. Moetakef and S. Stemmer, “Enhancing the electron
mobility in SrTiO3 with strain,” Appl. Phys. Lett., 98, 132102 (2011).
http://dx.doi.org/10.1063/1.3571447
D.J. Keeble, B. Jalan, L. Ravelli, W. Egger, G. Kanda, and S. Stemmer, “Suppression of
vacancy defects in epitaxial La-doped SrTiO3 films” Appl. Phys. Lett., 99. 232905 (2011).
http://dx.doi.org/10.1063/1.3664398
J. Son*, P. Moetakef*, B. Jalan*, O. Bierwagen*, N. J.Wright, R. Engel-Herbert and S.
Stemmer, “Epitaxial SrTiO3 films with electron mobilities exceeding 30,000 cm2/Vs,” Nat.
Mater., 9, 482 (2010), *Contributed equally. DOI: 10.1038/NMAT2750
16 d. Synergistic Activities
•
•
•
•
Professional Leadership and Service - Member of MRS Task force for National
Nanotechnology Initiative submitted to white house (NNI – 2010); Session chair at the
Electronic Materials and Applications (2010). Symposium co-organizer of Minnesota
Nanotechnology Conference (2012); Board member of American Vacuum Society local
Minnesota chapter (2011 to present), Symposium co-organizer for local MN AVS chapter
(2013-present), Symposium co-organizer for the 56th Electronic Materials Conference
(2014-present), Co-organizer of a focus session on the topic of “Complex Oxide
Interfaces and Heterostructures” at the APS march meeting (2015), Symposium coorganizer for the Electronic Materials Applications (2016), Co-organizer of the workshop
on oxide electronics, Chicago (WOE-2017).
Service to Scientific and Engineering Community - Reviewer for Journal of Electronic
Materials, Journal of Vacuum Science and Technology (JVST), Applied Physics Letter,
MRS symposium proceedings, Advanced Energy materials; Served as a judge at the
state science fair (for high school students), Minnesota academy of science, Member of
advisory board for vacuum technology for Normandale Community college, Minneapolis.
Creation and Dissemination of Scientific Knowledge – 25 refereed journal articles related
to thin films and heterostructures of complex oxides, defects in ceramics and electronic
properties. Over 25 technical presentations in national and international conferences and
universities including 18 invited talks.
Professional Society Memberships: Member of Materials Research Society (MRS),
American Physical Society, American Vacuum Society, and American Ceramic Society.
e. Collaborators and Other Affiliations
Collaborators and Co-Editors (preceding 48 months):
Prof. Chris Leighton (University of Minnesota), Prof. Renata Wentzcovitch (University of
Minnesota), Prof. Andre K. Mkhoyan (University of Minnesota); Prof. Brittany B. NelsonCheeseman, (University of St. Thomas), Prof. David K. Keeble (University of Dundee, UK),
Prof. Roman Engel-Herbert (Penn state), Prof. David Mandrus (University of Tennessee,
Knoxville), Dr. David J. Singh (ORNL), Prof. Kyle Chen (Cornell University), Prof. Wayne
Gladfelter (University of Minnesota).
Graduate Advisor:
Susanne Stemmer (University of California, Santa Barbara).
Thesis Advisor and Postgraduate-Scholar Sponsor (Past 5 years):
Current research group at UMN: 4 graduate students and 2 undergraduate researchers.
Graduate students: Andrew Xu, Koustav Ganguly, Tianqi Wang, Abhinav Prakash.
Undergraduate researchers: John Dewey (Mater. Sci.), Christopher Cheng (Mater. Sci.)
17